Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/382—Contact thermal transfer or sublimation processes
  • B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
  • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/382—Contact thermal transfer or sublimation processes
  • B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
  • B41M5/388—Azo dyes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/382—Contact thermal transfer or sublimation processes
  • B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
  • B41M5/39—Dyes containing one or more carbon-to-nitrogen double bonds, e.g. azomethine
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/913—Material designed to be responsive to temperature, light, moisture
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/914—Transfer or decalcomania

Definitions

• the present invention relates to a thermal transfer sheet, and more particularly, to provide a thermal transfer sheet capable of easily giving a recording material having excellent robustness to a material to be transferred.
• a sublimable dye is used as a recording agent, and this is carried on a base sheet such as paper to form a thermal transfer sheet and dyed with a sublimable dye.
• a sublimation transfer method is performed in which a sublimable dye is transferred to the material to be transferred by applying heat energy in a pattern form from the back side of the thermal transfer sheet by overlapping the material on the material to be transferred, such as a polyester woven cloth. Have been.
• the heat energy is applied for a relatively long time. As a result of the heating, relatively good dye transfer is achieved.
• thermal heads and the like have been used at high speeds, for example, using polyester sheets or paper-to-be-transferred dye-receiving layers.
• thermal energy it is necessary that the application of thermal energy be extremely short, on the order of seconds or less. Since the dye and the material to be transferred are not sufficiently heated, an image having a sufficient density cannot be formed.
• the above high-speed recording method has a low sublimation speed, so that an image having a satisfactory density cannot be formed as described above. Was something.
• thermo transfer sheets by applying heat energy in an extremely short time as described above, a clear image having a sufficient density is provided, and the formed image exhibits excellent various robustness.
• thermal transfer sheets there is a strong demand for the development of thermal transfer sheets.
• the present invention comprises a substrate sheet and a dye-supporting layer formed on one side of the substrate sheet, and the dye contained in the dye-supporting layer is represented by the following general formula (I). It is a thermal transfer sheet characterized by being a dye to be used.
• R in the above formula is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aryl group, a cycloalkyl group, an arylalkyl group, an alkoxy group, an acylamino group.
• Amino ' represents a substituent such as a carbonyl group
• ⁇ represents 1 or 2
• R 2 and R represent an alkyl group or a substituted alkyl group, and R and R may form a ring
• X represents a hydrogen atom or one or more substituents.
• the present invention comprises a substrate sheet and dye-bearing dust formed on one surface of the substrate sheet, wherein the dye contained in the dye-bearing layer is A thermal transfer sheet characterized by being a dye represented by the following general formula (II): ACN
• a in the above formula is a cyano group, an alkoxylcarbonyl group, an aryloxycarbonyl group, an alkylcarbamoyl group, an alkylcarbamoyl group, an arylalkyl group, an alkylcarboxylic group, an alkyl group.
• R ⁇ is a substituted or non-S-substituted alkyl, aralkyl or aryl group.
• R represents a substituted or unsubstituted alkyl group, an aralkyl group or an aryl group, and! ⁇ ⁇ And R 2 may form a 5- or 6-membered ring which may contain an oxygen atom or a nitrogen atom
• R is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent
• R 4 represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group, a nitro group, a cyano group, an acylamino group
• Z represents a hydrogen atom or an atom or 1 that forms a 5- or 6-membered ring with R ⁇ .
• n and m represent 1 or 2, respectively.
• the heat transfer sheet and the woven fabric as the material to be transferred are different from each other. It is essential that the dye used for this purpose does not have a sufficient density, and that the dye used for the transfer should be capable of transferring or translocating (that is, capable of transferring the space existing between the heat transfer sheet and the woven fabric).
• the thermal transfer sheet carrying such a dye By using a thermal transfer sheet carrying such a dye, even if heat energy is applied for a very short time, the used dye can easily transfer to the material to be transferred, and a high density and excellent robustness can be obtained. I knew that a recording ii image could be formed.
• a diazonium compound of 2-aminobenzothiazol or a derivative thereof is subjected to a cupping reaction with a coupler such as N, N-dialkylaniline or a derivative thereof. It is obtained by a conventionally known manufacturing method.
• R sigma is a hydrogen atom in, or 2 against ⁇ zone group - position of main butoxy, et butoxy, R and R are hydroxyl groups, amino groups, alkylamino groups, acylamino groups, sulfonylamino groups, aminocarbonyl groups, and alkoxy groups such as propoxy and butoxy groups.
• Methyl which may have a polar substituent such as a minosulfonyl group, an alkoxycarbonyl group, an alkoxysulfonyl group, a cyano group, an alkoxy group, a phenyl group, a cycloalkyl group, a halogen atom or a nitro group; Echiru, propyl, hexyl butyl, pentyl, heptyl, Okuchiru, Bruno alkenyl, decyl, ⁇ Ndeshiru, dodecyl, the Flip such Kisadeshiru of ⁇ Itaru c 2 (1 alkyl X is a hydrogen atom, or an alkoxy group such as a methoxy, ethoxy, propoxy, or butoxy group at the 6-position, and the dye has a fraction of at least 320, more preferably Or a group selected by JS such that the molecular weight is at least 350.
• R ⁇ and X are a lower alkoxy group
• R 2 and R 3 is a dye of the alkyl group having a carbon number of 1 to 2 0 substituted with hydroxyl or cyano ⁇ .
• groups other than hydrogen such as a substituted or unsubstituted alkyl group, are selected as R ⁇ to R 3 and X.
• the molecular weight of the dye increases, and the molecular weight of the dye exceeds 322 or 350.
• the melting points of these dyes tend to decrease, and when such dyes are used as dyes for thermal transfer sheets, they can be heated for a very short time using a thermal head or the like. It has been found that the heat transfer speed of the dye from the thermal transfer sheet to the material to be transferred increases, and that both images provide excellent fastness, especially excellent storage stability and light fastness.
• a dye having a molecular weight of less than 300 can satisfy the coloration density and the like, but the storage stability and light fastness of the formed image are satisfactory. Was inadequate.
• the above preferred dyes are methylethyl ketone, toluene, ethanol, isopropyl alcohol, cyclohexanone, ethyl acetate, etc., or a mixture thereof used in the preparation of the thermal transfer sheet.
• the solubility in general-purpose organic solvents such as base solvents has been significantly improved, and the dye formed on the thermal transfer sheet has no or low crystallinity in the loading calendar As in the case of the conventional dye, the dye can be easily transferred to the material to be transferred with a much smaller amount of applied heat compared to the existing state having high crystallinity.
• Table A1 shows the substitutions SR i to R 3 , n and X in the general formula (I).
• the dye used in the second embodiment of the present invention is tl A dihydrobenzothiophene-1, 1-dioxide derivative represented by the following general formula ( ⁇ ) and a nitroso compound represented by the following general formula (IV) in the presence of a solvent. It can be easily produced by dehydration condensation.
• Preferred dyes in the second aspect of the present invention are those having a molecular weight of at least 400, and with respect to the substituents, Z may have a hydrogen atom and R 1 and R 2 or R 2 may have a hydroxyl group.
• hydroxyl group substituent R E to R 4 and A A Mi amino group, alkylamine Mi amino group, Ashirua Mi Bruno S, Suruhonirua Mi amino group, ⁇ Mi Roh carbonyl group, A Mi A group having a polar group such as a sulfonyl group, an alkoxycarbonyl group, an alkoxysulfonyl group, a cyano group, an alkoxy group, a phenyl group, a cycloalkyl group, a halogen atom or a nitro group. is there.
• the thermal transfer sheet of the present invention is characterized by using the specific dye as described above, and the other configuration may be the same as the configuration of a conventionally known thermal transfer sheet.
• the substrate sheet used in the thermal transfer sheet of the present invention containing the above dye may be any conventionally known one having a certain degree of heat resistance and strength.
• 0.5 to 50 m preferably: 3 to 10 m thick paper, various processed papers, polyester films, polystyrene films, poly films Propylene innolem, polysnolephone innolem, polycarbonate film, aramid film, poly.vininoleanolecole innolem, cellophane, etc., particularly preferred Shii ones dye ⁇ provided in c above such substrates Sea Bok surface is Po Li Esuterufu I Noremu ⁇ , the general formula (I) or ([pi) of the dye of Nin'okota by Sunda - carrying resin Layer.
• binder resin for supporting the dye any of the conventionally known binder resins can be used, and preferred ones are exemplified by ethyl cellulose, hydroxymethyl, cinnamon, and ethyl hydride.
• Cellulose-based resins such as roxycellulose, hydroxypropyl selenololose, methylcellulose, cellulose acetate, cellulose acetate butyrate, etc., polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyester Vinyl-based resins such as vinyl acetate acetal, polyvinyl alcohol, polyacrylamide, etc. are available.
• polyvinyl butyral and polyvinyl acetal are particularly preferred in terms of heat resistance, dye migration, and the like.
• the dye-carrying layer of the thermal transfer sheet of the present invention may be composed of a material formed from the above-mentioned materials (and, if necessary, various additives similar to those known in the art). is there.
• Such a dye-carrying layer is preferably prepared by adding the above-mentioned dye, binder resin and other optional components to a suitable solvent and dissolving or dispersing each component to prepare a coating solution for forming a supporting layer or an ink. Then, this is applied onto the above-mentioned base sheet and dried to form the base sheet.
• the support layer thus formed has a thickness of about 0.2 to 5.0, preferably about 4 to 2.0 ⁇ m, and the dye in the support layer is a small amount of the support layer. It is preferably present in an amount of 5 to 70% by weight, preferably 10 to 60% by weight.
• the thermal transfer sheet of the present invention as described above is sufficiently useful for thermal transfer as it is, but further carries a dye.
• An anti-adhesion layer that is, a release layer may be provided on the surface.
• the release layer As the release layer, the effect of inviting is shown even by simply applying an anti-adhesive inorganic powder. 0.01 to 5 m, preferably 0.05 to 2 from resin having excellent mold releasability such as a polymer, an acrylic polymer, and a fluoropolymer. It can be formed by providing a u.m release layer.
• the inorganic powder or the releasable polymer as described above has a sufficient effect even if it is included in the material-carrying material.
• a thermal head is provided on the back surface of such a thermal transfer sheet.
• a heat-resistant layer may be provided to prevent adverse effects due to heat of the metal.
• the transfer material used for forming an image using the thermal transfer sheet as described above may be any material as long as its recording surface has a dye-accepting property for the dye.
• a dye receiving layer may be formed on at least one surface thereof.
• Examples of the transfer-receiving material that does not require the formation of the dye-receiving layer include, for example, a polyolefin resin such as polypropylene, a polyvinyl chloride, and a halogenated poly (vinylidene chloride) such as polyvinylidene chloride.
• a polyolefin resin such as polypropylene, a polyvinyl chloride, and a halogenated poly (vinylidene chloride) such as polyvinylidene chloride.
• Polymers such as vinyl polymers, polyvinyl acetates, and polyacrylic esters, etc.Polyesters such as polyethylene terephthalate, polybutylene terephthalate, etc.
• Resins, polystyrene Resin, ionomer resin, cellulose diacetate, etc. of resin such as ethylene resin, polyamide resin, ethylene and propylene, and other vinyl monomers.
• a sheet or a film made of polyester or a paper provided with a polyester layer is particularly preferred.
• the dyeing resin solution or dispersion as described above is applied to the recording surface and dried, or by La Mi Natick door a resin film Lum of, O 0 can Toka and the transfer material
• a dye receiving layer may be formed on the surface of the transfer material from a resin having a better dyeing property as in the case of the paper.
• Dye receiving formed in this way May be formed from a single material or from a plurality of materials, and it is natural that ill may include various additives as long as the intended purpose is not hindered.
• Such a dye-receiving layer has a force ⁇ any thickness, generally 3 to 50 / m. Further, such a dye receiving layer is preferably a continuous coating, but may be formed as a discontinuous coating using a resin emulsion or a resin dispersion.
• Such a material to be transferred is basically as described above, and can be used satisfactorily until then. Let In this way, even if the temperature at the time of thermal transfer is further increased, the sticking between the thermal transfer sheet and the material to be transferred can be prevented, and thermal transfer excellent in ill can be performed. Particularly preferred is finely divided silica.
• a particularly preferred release polymer is a cured product of a silicone compound, for example, a cured product of an epoxy-modified silicone oil and an amino-modified silicone oil.
• a release agent preferably accounts for about 0.5 to 30% by weight of the weight of the dye receiving layer.
• the transfer material to be used may have the anti-stick effect J by adhering the inorganic powder as described above to the surface of the dye-receiving surface, and has excellent releasability as described above.
• a layer made of a release agent may be provided.
• Such a release layer exhibits a sufficient effect at a thickness of about 0.017 to 5 m, and prevents the heat transfer sheet from adhering to the dye receiving layer, while providing a single layer of the dye. It is possible to improve the receptivity.
• the means for applying the thermal energy to ffl when performing the thermal transfer using the thermal transfer sheet of the present invention as described above and the recording material as described above is a conventionally known applying means. Either of them can be used.
• a thermal printer for example, a video printer V ⁇ -1 ⁇ ⁇ manufactured by ⁇ ⁇ ⁇ ); By controlling the recording time, 5 to
• the dye used in the construction of the thermal transfer sheet of the present invention is a sublimable dye (molecular weight of about 15 to 31) used in the thermal transfer sheet of the prior art. Despite having a very high molecular weight, it has a specific structure and has a substituted S at a specific position. 3 ⁇ 4Excellent heat transferability, dyeability to transfer material and proper It shows color properties, and does not transfer to the material to be transferred after transfer and does not bleed out on the surface. Therefore, the image formed by using the thermal transfer sheet of the present invention has excellent robustness, particularly migration resistance and stain resistance, and thus the sharpness of the formed image is lost even after long-term storage. And no contamination of other articles was solved, and the various problems of the prior art were solved.
• the dye at least one of R 3 to R 3 in the general formula (I) or at least one of R ⁇ to R 4 , ⁇ and Z in the formula ( ⁇ ) has a polarity.
• the fastness as described above was remarkable.
• Such an excellent effect, which cannot be considered in the prior art, is particularly apparent in the case where the material receiving part of the substance is a substance such as a polyester because the dye has the polarity S because the dye has the polarity S.
• Polyester i It is considered that the polymer is fixed in the polyester by some action due to the correlation with the ester bond.
• a solution prepared by dissolving 7 g of sodium nitrite in 20 mJ of water is gradually added to diazotize the solution.
• a small amount of sulfamic acid is added and filtered to prepare a diazo solution.
• the dye-supported layer forming I Nki composition having the following composition was prepared, the 6 ⁇ m ⁇ Po Re ethylene Les Nterefu data, single Tofui Lum of which has been subjected to heat treatment to the back, dry coating amount 1. O g Zm 2 The resultant was coated and dried to obtain thermal transfer sheets of the present invention and comparative examples.
• a sheet of paper (Oji Chemical Co., Ltd., Fupo FPG 15 U) was used as the base sheet.
• the coating liquid was applied at a rate of 10.0 g Zm 2 when dried, and dried at 1 ° C. for 30 minutes to obtain a transfer-receiving material.
• Polyester resin (Vylon200, Toyobo)
• Hexanone (weight ratio 4: 4: 2) 102.0 parts The above heat transfer sheets of the present invention and the comparative example and the above; ! With the thermal transfer sheet on the back side, and record with the thermal head under the conditions of the applied voltage of the head from the back of the thermal transfer sheet of 10 V and the printing time of 4.0 and 0 msec. I got the result.
• Dye A I Disperse Red 1 min S 14)
• Dye A n Disperse Bioviolet 1 (Molecular Weight
• the color density described above is a value measured with a densitometer RD-9918 manufactured by Macbeth I: U.S.A.
• the storability was as follows: after releasing both images in a 50 ° C atmosphere, the sharpness of both images did not change, and the images were printed on paper. If the white paper is not colored even by rubbing, it is marked as ⁇ . If the crab sharpness is lost and the white paper is slightly colored, it is marked as ⁇ . If the sharpness is lost and the white paper is colored, In the case of ⁇ , the image became unclear and the white paper marked markedly colored was indicated by X.
• the light fastness was evaluated as ⁇ when the initial fastness of the JIS L 0841 dini exposure method was 3 or higher, ⁇ when the initial fastness was about 3 or higher, and X when the initial fastness was about 3 or lower. .
• An ink composition for forming a dye-carrying layer having the following composition was applied to a 6 m ⁇ polyethylene terephthalate film having a heat-treated surface, and dried and applied ⁇ 1 to 1 g. / m-naaru Coating and drying were performed in the same manner to obtain a thermal transfer sheet of the present invention.
• Polyester resin (Vylon200, manufactured by Toyobo)
• Comparative Example B5 Disuse Biolet 4 The color density in the above was measured with a densitometer RD-9918 manufactured by Macbeth, USA (straight).
• the thermal transfer sheet of the present invention can be widely used as an image forming material by a thermal transfer method with a thermal head.

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• Health & Medical Sciences (AREA)
• Heart & Thoracic Surgery (AREA)
• Vascular Medicine (AREA)
• Cardiology (AREA)
• Oral & Maxillofacial Surgery (AREA)
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• Engineering & Computer Science (AREA)
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• Life Sciences & Earth Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Public Health (AREA)
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• Thermal Transfer Or Thermal Recording In General (AREA)

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• 1989
  • 1989-08-29 DE DE68926164T patent/DE68926164T2/de not_active Expired - Fee Related
  • 1989-08-29 US US07/474,052 patent/US5286705A/en not_active Expired - Fee Related
  • 1989-08-29 EP EP89909617A patent/EP0423336B1/de not_active Expired - Lifetime
  • 1989-08-29 WO PCT/JP1989/000877 patent/WO1990002047A1/ja active IP Right Grant

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